Wei-Wei Fu

Syntheses, crystal structures and luminescence of zinc(II) and cadmium(II) complexes with 4′-substituted 2,2′:6′,2″-terpyridines

Four terpyridine coordination complexes, [Zn(meophtpy)2]·(ClO4)2·(H2O) (1), [Cd(meophtpy)2]·(ClO4)2 (2), [Zn(nh2phtpy)2]·(ClO4)2 (3), and [Cd(nh2phtpy)2]·(ClO4)2 (4) (meophtpy = 4′-(p-methoxylphenyl)-2,2′:6′,2″-terpyridine, nh2phtpy = 4′-aminophenyl-2,2′:6′,2″-terpyridine), were synthesized using the solvothermal method. These complexes have been characterized by IR spectra, elemental analyses, and X-ray diffraction. In all these complexes, the metal ions are coordinated by six nitrogens from two terpyridines. 3-D networks have been constructed by hydrogen bonds and π–π interactions. The luminescence of these four complexes has been investigated in the solid state at room temperature. Graphical abstract Four Zn(II) and Cd(II) complexes with two kinds of terpyridines have been synthesized and characterized. All these complexes are six N coordinated with two terpyridines. 3-D networks have been formed with hydrogen bonds and π–π interactions. The luminescence properties have been studied and all these ligands and complexes can be used as luminescence materials.

Hydrothermal syntheses, crystal structures, and magnetic properties of three manganese(II) complexes based on 4′-substituted 2,2′:6′,2″-terpyridine ligands

Three manganese coordination compounds, [Mn(Meophtpy)2] · 2ClO4 (Meophtpy = 4′-(4-methoxylphenyl)-2,2′:6′,2″-terpyridine) (I), [Mn(Ftpy)2](ClO4)2 (Ftpy = 4′-(2-furyl)-2,2′:6′,2″-terpyridine) (II) and [Mn(m-ClPhtpy)2] · 2ClO4 (m-ClPhtpy = 4′-(3-chlorophenyl)-2,2′:6′,2″-terpyridine) (III), have been synthesized by hydrothermal methods and characterized by IR, elemental analysis, powder and single-crystal X-ray diffraction analyses (CIF files CCDC nos. 945032 (I), 945033 (II), 945034 (III)). In most cases, the face-to-face interactions between pyridyl rings or phenyl rings facilitate the construction of 3D network in the crystal for all three complexes. The magnetic properties of three complexes have been investigated.

A new two-dimensional extended adenine and thiophenecarboxylate mixed-ligand zinc(II) complex: synthesis, structure, thermostability and luminescent properties.

The design and preparation of crystalline polymeric materials has attracted increasing attention due to their diverse applications as functional materials in gas storage, separation, catalysis, sensing and photoluminescence. The judicious selection of organic linkers is critical for varying the coordination behaviour of the metal ions and determining the overall characteristics of the networks. A new adenine-based Zn(II) coordination polymer, [Zn(C6H2O4S)(C5H5N5)]n or [Zn(tdc)(9H-ade)] (H2tdc is thiophene-2,5-dicarboxylic acid and ade is adenine), has been prepared hydrothermally and the crystal structure exhibits in its packing two-dimensional (4,4) grid sheets parallel to the ab plane, featuring two distinct square cavities delimited by the two types of ligands and the Zn(II) ions with the dimensions 6.6 × 6.6 and 10.2 × 10.2 Å (based on the Zn...Zn distance). The title complex shows enhanced photoluminescence at 378 nm compared to the free ligands, suggesting that the coordination of H2tdc or adenine to the metal centre effectively increases the rigidity of the ligands and reduces the energy loss by radiative decay of intraligand excited states.

Syntheses and crystal structures of [Fe(m-NO2phtpy)2](ClO4)2 and [Fe(m-Clphtpy)2](ClO4)2 (m-NO2phtpy = 4′-(3-nitrophenyl)-2,2′:6′,2″-terpyridine and m-Clphtpy = 4′-(3-chlorophenyl)-2,2′:6′,2″-terpyridine)

Two iron compounds [Fe(m-NO2phtpy)2](ClO4)21 and [Fe(m-Clphtpy)2](ClO4)22 are synthesized and their structures are determined by single crystal X-ray diffraction. Crystal data for 1 are: orthorhombic, space group Pcca, a = 25.471(4) Å, b = 10.8182(18) Å, c = 14.682(2) Å, Z = 4. Crystal data for 2 are: orthorhombic, space group Pnna, a = 14.521(2) Å, b = 23.980(4) Å, c = 23.142(4) Å, and Z = 8. The iron atoms are coordinated by six N atoms from two terpyridines in both compounds. These two compounds are all linked by hydrogen bonds with C as donor and O as acceptor into a 3D network for 1 and a 2D network for 2. If viewed along the c direction in 1 and the a direction in 2, both compounds show the ordered figure with terpyridine overlapped as a square and the phenyl rings overlapped as a rectangle or a square.

New Co(II) And Mn(II) Complexes with 4′-Substituted 2,2′:6′,2″-Terpyridine Ligands

Three Co(II) complexes [Co(meophtpy)2](ClO4)2·2CH3CN (1), [Co(nh2phtpy)2](ClO4)2·2CH3CN (2), [Co(ftpy)2](ClO4)2·2CH3CN (3) and three Mn(II) complexes [Mn(nme2phtpy)2]·(ClO4)2·2CH3CN (4), [Mn(ftpy)2](ClO4)2·CH3CN (5), [Mn(meophtpy)(H2O)(NO3)2]·CH3CN (6) (meophtpy, 4′-(4- methoxyphenyl)-2,2′:6′,2″-terpyridine; nh2phtpy, 4′-(4-aminophenyl)-2,2′:6′,2″-terpyridine; ftpy, 4′-(furan- 2-yl)-2,2′:6′,2″-terpyridine; nme2phtpy, 4′-(4-(N,N-dimethylamino)phenyl)-2,2′:6′,2″-terpyridine) are synthesized and their structures are determined by single crystal X-ray diffraction. Crystal data for 1 are: monoclinic, space group C2/c, a = 14.4781(5) Å, b = 16.2221(7) Å, c = 21.3617(9) Å, and Z = 4. For 2: monoclinic, space group C2/c, a = 14.554(6) Å, b = 15.239(6) Å, c = 21.754(9) Å, and Z = 4. For 3: monoclinic, space group C2/c, a = 14.5285(16) Å, b = 15.3234(16) Å, c = 21.154(2) Å, and Z = 4. For 4: triclinic, space group P-1, a = 12.132(5) Å, b = 12.536(5) Å, c =17.840(10) Å, and Z = 2. For 5: triclinic, space group P-1, a = 9.993(10) Å, b = 13.950(13) Å, c = 15.511(15) Å, and Z = 2. For 6: monoclinic, space group Pc, a = 12.402(7) Å, b = 12.919(8) Å, c = 7.893(5) Å, and Z = 2. In complexes 1–5, Co(II) or Mn(II) ions are coordinated by six N atoms from two terpyridine moieties. In complex 6 the Mn(II) atom coordinates only one terpyridine ligand. All these complexes are linked by hydrogen bonds and face-to-face π–π interactions into three-dimensional networks. In complexes 4–6 the available solvent areas imply their potential applications in gas adsorption or catalysis.

Assembly of ZnII and CdII coordination polymers with different dimensionalities based on the semi-flexible 3-(1H-benzimidazol-2-yl)propanoic acid ligand

Two unprecedented two-dimensional and one-dimensional ZnII and CdII complexes based on a semi-flexible ligand have been structurally identified.

Effect of solvent on the crystal structures of copper(II) complexes based on 4′-(4-methoxyphenyl)-2,2′:6′,2″-terpyridine and 4′-(3-chlorophenyl)-2,2′:6′,2″-terpyridine

Four homoleptic copper(II) complexes, [Cu(Meophtpy)2](ClO4)2 (Meophtpy = 4′-(4-methoxylphenyl)- 2,2′:6′,2″-terpyridine) (I), [Cu(Meophtpy)2](ClO4)2 · 2H2O (II), [Cu2(m-Clphtpy)4](ClO4)4 (m-ClPhtpy = 4′-(3-chlorophenyl)-2,2′:6′,2″-terpyridine) (III), and [Cu2(m-ClPhtpy)4](ClO4)4 (IV) have been synthesized by hydrothermal methods and characterized by IR, elemental analysis and single crystal X-ray diffraction (CIF files CCDC nos. 963375 (I), 885457 (II), 963377 (III), and 963376 (IV)). Complex II is a polymorph of I and complex IV is a polymorph of III. All these complexes are obtained with 95% ethanol solution or 50% ethanol solution and the solvent control on the crystallization are obviously found. In all complexes, the face-to-face interactions between pyridyl rings or phenyl rings facilitate the construction of 3D network in the crystal in addition to hydrogen bonds. The fluorescence properties of these complexes have been investigated.

An infinite two-dimensional hybrid water–chloride network in a 4′-(furan-2-yl)-2,2′:6′,2′′-terpyridine nickel(II) matrix

An unprecedented two-dimensional water–chloride anionic {[(H2O)10Cl2]2−}n network has been structurally identified in a hydrophobic matrix of the nickel(II) complex [Ni(ftpy)2]Cl2·10H2O [ftpy = 4′-(furan-2-yl)-2,2′:6′,2′′-terpyridine].

(4,6‐Dimethyl‐2‐sulfanylidenepyrimidin‐1‐ium) trichlorido(thiourea‐κS)zinc(II)

The title compound, (C6H9N2S)[ZnCl3{SC(NH2)2}], exists as a zincate where the zinc(II) centre is coordinated by three chloride ligands and a thiourea ligand to form the anion. The organic cation adopts the protonated 4,6-dimethyl-2-sulfanylidenepyrimidin-1-ium (L) form of 4,6-dimethylpyrimidine-2(1H)-thione. Two short N-H···Cl hydrogen bonds involving the pyrimidine H atoms and the [ZnCl3L](-) anion form a crystallographically centrosymmetric dimeric unit consisting of two anions and two cations. The packing structure is completed by longer-range hydrogen bonds donated by the thiourea NH2 groups to chloride ligand hydrogen-bond acceptors.